Synthesis, Photoluminescence, and Electroluminescence of Phosphorescent Dipyrido[3,2-a;2'3'-c]phenazine-Platinum(II) Complexes Bearing Hole-Transporting Acetylide Ligands.

In this study, novel phosphorescent dipyrido[3,2-a;2'3'-c]phenazine (dppz)-platinum(II)-phenylacetylide complexes were developed to fabricate non-doped organic light-emitting diodes (OLED) by solution-processing. To facilitate the charge carrier injection into the emitting layer (EML), 3,6-di-tert-butylcarbazole-functinalized phenylacetylides were employed. As for the dppz ligand, 9,9-dihexylfluoren-2-yl and 4-hexylthiophen-2-yl side-arms were introduced to the 2,7-positions, which led to reddish orange and red photoluminescence (PL), respectively, in solution and film states (PL wavelength: ca. 600 and ca. 625 nm, respectively). The carbazole-appended phenylacetylide ligands hardly affected the emission color, although unsubstituted phenylacetylides gave rise to aggregate- or excimer-based near-infrared PL with a low quantum yield. Two types of non-doped OLEDs were fabricated: single-layer and multilayer devices. In both devices, the organic layers were fabricated by spin-coating, and the EML consisted of a neat film of the corresponding platinum(II) complex. Therein, electroluminescence spectra corresponding to those of PL were observed. The single-layer devices exhibited low device efficiencies due to a deteriorated charge carrier balance. The multilayer devices possessed hole- and electron-transporting layers on the anode and cathode sides of the EML, respectively. Owing to an improved charge carrier balance, the multilayer devices exhibited higher device performance, affording considerably improved values of luminance and external quantum efficiency.

Crystal structure of (µ-hydrogen di-sulfato)-µ-oxido-bis-[(4,4'-di-tert-butyl-2,2'-bi-pyridine)-oxidovanadium(IV/V)] aceto-nitrile monosolvate.

The dinuclear oxidovanadium(IV/V) complex, [V2(HS2O8)O3(C18H24N2)2]·CH3CN or [V2O2(µ-O)(µ-H(SO4)2)(4,4'-tBubpy)2]·CH3CN (4,4'-tBubpy = 4,4'-di-tert-butyl-2,2'-bi-pyridine), has crystallographic C 2 symmetry and exhibits a distorted octa-hedral geometry around the vanadium center, where the two 4,4'-tBubpy ligands are nearly orthogonal to each other. The two vanadium ions are linked by an oxo anion and a unique protonated sulfate anion [H(SO4)2 3-]. In the crystal, inter-molecular C-H⋯π and π-π inter-actions between the 4,4'-tBubpy ligands are present, leading to a three-dimensional network.

Innovative green oxidation of amines to imines under atmospheric oxygen.

In recent years, the development of environmentally benign molecular construction methods has been of great importance, and especially, resource recycling, high atomic efficiency, and low environmental impact are in high demand. From this point of view, attention has also been focused on the development of one-pot synthesis of pharmaceuticals and functional molecules. Imines are excellent synthetic intermediates of these useful molecules, and the environmentally friendly oxidative synthesis of imines from amines has been energetically developed using oxygen (or air), which is abundantly available on the Earth, as an oxidant. This review focuses on the latest innovative and green oxidation systems of amines to imines under atmospheric oxygen, and their application to one-pot/eco-friendly and sustainable synthesis of pharmaceuticals and functional molecules. In particular, catalytic systems that activate molecular oxygen are categorized and described in detail as transition metal catalytic systems, photoirradiated catalytic systems, and organocatalytic systems.

Potential of a Novel Chemical Compound Targeting Matrix Metalloprotease-13 for Early Osteoarthritis: An In Vitro Study.

Osteoarthritis is a progressive disease characterized by cartilage destruction in the joints. Matrix metalloproteinases (MMPs) and a disintegrin and metalloproteinase with thrombospondin motifs (ADAMTSs) play key roles in osteoarthritis progression. In this study, we screened a chemical compound library to identify new drug candidates that target MMP and ADAMTS using a cytokine-stimulated OUMS-27 chondrosarcoma cells. By screening PCR-based mRNA expression, we selected 2-(8-methoxy-2-methyl-4-oxoquinolin-1(4H)-yl)-N-(3-methoxyphenyl) acetamide as a potential candidate. We found that 2-(8-methoxy-2-methyl-4-oxoquinolin-1(4H)-yl)-N-(3-methoxyphenyl) acetamide attenuated IL-1ß-induced MMP13 mRNA expression in a dose-dependent manner, without causing serious cytotoxicity. Signaling pathway analysis revealed that 2-(8-methoxy-2-methyl-4-oxoquinolin-1(4H)-yl)-N-(3-methoxyphenyl) acetamide attenuated ERK- and p-38-phosphorylation as well as JNK phosphorylation. We then examined the additive effect of 2-(8-methoxy-2-methyl-4-oxoquinolin-1(4H)-yl)-N-(3-methoxyphenyl) acetamide in combination with low-dose betamethasone on IL-1ß-stimulated cells. Combined treatment with 2-(8-methoxy-2-methyl-4-oxoquinolin-1(4H)-yl)-N-(3-methoxyphenyl) acetamide and betamethasone significantly attenuated MMP13 and ADAMTS9 mRNA expression. In conclusion, we identified a potential compound of interest that may help attenuate matrix-degrading enzymes in the early osteoarthritis-affected joints.

Transition-Metal-Free Synthesis of Unsymmetrical Diaryl Tellurides via SH2 Reaction of Aryl Radicals on Tellurium.

Although diaryl tellurides are parent organotellurium compounds, their synthesis methods, especially for unsymmetrical ones, are limited. This may be due to the instability of diaryl tellurides and their synthesis intermediates under reaction conditions. Radical reactions are known to exhibit excellent functional group selectivity; therefore, we focused on a bimolecular homolytic substitution (SH2) reaction between the aryl radical and diaryl ditelluride. Aryl radicals are generated from arylhydrazines in air and captured by diaryl ditellurides, resulting in a selective formation of unsymmetrical diaryl tellurides with high yields. The electronic effects of the substituents on both arylhydrazines and diaryl ditellurides on the SH2 reaction of tellurium are also discussed in detail.

Photoinduced Bisphosphination of Alkynes with Phosphorus Interelement Compounds and Its Application to Double-Bond Isomerization.

The addition of interelement compounds with heteroatom-heteroatom single bonds to carbon-carbon unsaturated bonds under light irradiation is believed to be an atomically efficient method to procure materials with carbon-heteroatom bonds. In this study, we achieved the photoinduced bisphosphination of alkynes using the phosphorus interelement compound, tetraphenyldiphosphine monosulfide (1), to stereoselectively obtain the corresponding (E)-vic-1,2-bisphosphinoalkenes, which are important transition-metal ligands. The bisphosphination reaction was performed by mixing 1 and various alkynes and then exposing the mixture to light irradiation. Optimization of the conditions for the bisphosphination reaction resulted in a wide substrate range and excellent trans-selectivity. Moreover, the completely regioselective introduction of pentavalent and trivalent phosphorus groups to the terminal and internal positions of the alkynes, respectively, was achieved. We also found that the novel double-bond isomerization reaction of the synthesized bisphosphinated products occurred with a catalytic amount of a base under mild conditions. Our method for the photoinduced bisphosphination of carbon-carbon unsaturated compounds may have strong implications for both organic synthesis and organometallic and catalyst chemistry.

A two-phase bromination process using tetraalkylammonium hydroxide for the practical synthesis of α-bromolactones from lactones.

A simple and efficient method for α-brominating lactones that affords α-bromolactones under mild conditions using tetraalkylammonium hydroxide (R4N+OH-) as a base was developed. Lactones are ring-opened with Br2 and a substoichiometric amount of PBr3, leading to good yields of the corresponding α-bromocarboxylic acids. Subsequent intramolecular cyclization over 1 h using a two-phase system (H2O/CHCl3) containing R4N+OH- afforded α-bromo lactones in good yields. This method can be applied at the 10 mmol scale using simple operations. α-Bromo-δ-valerolactone, which is extremely reactive and difficult to isolate, could be isolated and stored in a freezer for about one week using the developed method. Optimizing the solvent for environmentally friendly large-scale syntheses revealed that methyl ethyl ketone (MEK) was as effective. In addition, in situ-generated α-bromo-δ-valerolactone was directly converted into a sulfur-substituted functional lactone without difficulty by reacting it with a sulfur nucleophile in one pot without isolation. This new bromination system is expected to facilitate the industrial use of α-bromolactones as important intermediates.

Excellent Catalytic Performances of a Au/C-CuO Binary System in the Selective Oxidation of Benzylamines to Imines under Atmospheric Oxygen.

A green method of the oxidation of benzylamines to imines was developed using a novel binary system of Au/C-CuO. This system was evaluated under atmospheric oxygen, and the corresponding imines were obtained in up to 100% yields by loading 0.006 mol % of Au/C and 1.25 mol % of CuO under mild conditions. This system was also successfully applied to the syntheses of N-containing functional molecules, as well as that of imines on the scale of several grams. Furthermore, the turnover number of the system (more than 8000 times on a gold basis) as well as its ability to be reused more than 10 times for benzylamine oxidation demonstrates the excellent durability and recyclability of the developed system.

Clarification on the Reactivity of Diaryl Diselenides toward Hexacyclohexyldilead under Light.

In this study, the reactivity of organochalcogen compounds toward a representative alkyl-lead bond compound under light was investigated in detail. Under light irradiation, the Cy-Pb bond of Cy6Pb2 (Cy = cyclohexyl) undergoes homolytic cleavage to generate a cyclohexyl radical (Cy•). This radical can be successfully captured by diphenyl diselenide, which exhibits excellent carbon-radical-capturing ability. In the case of (PhS)2 and (PhTe)2, the yields of the corresponding cyclohexyl sulfides and tellurides were lower than that of (PhSe)2. This probably occurred due to the low carbon-radical-capturing ability of (PhS)2 and the high photosensitivity of the cyclohexyl-tellurium bond.

Transition-Metal-Catalyzed Diarylation of Isocyanides with Triarylbismuthines for the Selective Synthesis of Imine Derivatives.

The transition-metal-catalyzed diarylation of isocyanides with triarylbismuthines was investigated in detail, and rhodium catalysts such as [RhCl(nbd)]2 were found to selectively afford N-alkyl diaryl ketimines. On the other hand, palladium-catalyzed diarylation proceeded with the incorporation of two molecules of isocyanide, preferentially yielding N,N'-dialkyl or N,N'-diaryl α-diimines. In addition, a cascade synthesis of 2,3-diarylquinoxalines starting from the palladium-catalyzed diarylation of isocyanides with triarylbismuthines was successfully achieved.

Oxidative Synthesis of Acid Blue 7 Dye Catalyzed by CuO/Silicotungstic Acid in Water-Phase.

A catalytic oxidation reaction for Acid Blue 7 dye synthesis was evaluated in water. Without lead oxide or manganese oxide derivatives as oxidants, polyoxometalate catalysts were investigated to reduce the usage of harmful heavy metal. A catalyst was prepared by mixing silicotungstic acid with copper oxide, and aqueous hydrogen peroxide (30%) was used as an oxidizing agent. This reaction proceeded to produce Acid Blue 7 from the corresponding leuco acid after 45 min at 95 °C and was viable for a 10 g-scale synthesis.

One-Pot Construction of Diverse ß-Lactam Scaffolds via the Green Oxidation of Amines and Its Application to the Diastereoselective Synthesis of ß-Amino Acids.

In this study, a simple one-pot construction of ß-lactam scaffolds was successfully achieved via 4,6-dihydroxysalicylic acid-catalyzed organocatalytic oxidation of amines to imines using molecular oxygen. Although some imines are highly unstable and difficult to isolate by conventional methods, the organocatalytic oxidation of amines described herein, followed by their direct reaction with acyl chlorides in the presence of a base, afforded a series of new ß-lactam derivatives with excellent cis selectivity, which could not be synthesized and isolated by previously reported methods. Thus, this one-pot protocol will be one of the powerful methods applicable to the synthesis of various potential drug candidates and functional molecules. Furthermore, the subsequent hydrolysis of these ß-lactams successfully afforded the corresponding ß-amino acids as almost single diastereomers in up to 99% yields.

Highly regio- and stereoselective phosphinylphosphination of terminal alkynes with tetraphenyldiphosphine monoxide under radical conditions.

The homolytic cleavage of the PV(O)-PIII bond in tetraphenyldiphosphine monoxide simultaneously provides both pentavalent and trivalent phosphorus-centered radicals with different reactivities. The method using V-40 as an initiator is successfully investigated for the regio- and stereoselective phosphinylphosphination of terminal alkynes giving the corresponding trans-isomers of 1-diphenylphosphinyl-2-diphenylthiophosphinyl-1-alkenes in good yields. The protocol can be applied to a wide variety of terminal alkynes including both alkyl- and arylalkynes.

Au/Ag/Cu-Mixed Catalysts for the Eco-Friendly Oxidation of 5-Hydroxymethylfurfural and Related Compounds to Carboxylic Acids under Atmospheric Oxygen in Water.

A green method for the oxidation of alcohols to carboxylic acids was developed using a novel co-catalytic system based on gold, silver, and copper catalysts. This reaction system was conducted under atmospheric oxygen in water and mild conditions to selectively oxidize 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid, as a building block for polyethylene furanoate, which is a 100% bio-based, future alternative to the petroleum-based polyethylene terephthalate. Furthermore, various primary alcohols were conveniently oxidized to their corresponding carboxylic acids in up to quantitative yields.

trans-Bis[8-(benzyl-sulfan-yl)quinoline-κ2 N,S]di-chlorido-cobalt(II).

The title di-chloro-cobalt(II) complex, trans-[CoCl2(1)2] [1 = 8-(benzyl-sulfanyl)-quinoline, C16H13NS], has a central CoII atom (site symmetry ) that exhibits a distorted octa-hedral coordination geometry and is coordinated by two N and two S atoms from the bidentate N,S-ligand (1) situated in an equatorial plane and two Cl atoms in the axial positions. Complexes are linked by weak inter-molecular C-H⋯π inter-actions between the 8-(benzyl-sulfanyl)-quinoline ligands, forming a chain extending along the a-axis direction.

Metal-Free Synthesis of 2-Substituted Quinazolines via Green Oxidation of o-Aminobenzylamines: Practical Construction of N-Containing Heterocycles Based on a Salicylic Acid-Catalyzed Oxidation System.

Conventional quinazoline synthesis methods involve a highly multistep reaction, and often require excess amounts of substrate to control the product selectivity, leading to significant resource wastage. Hence, in this study, from the viewpoint of green chemistry, we developed a novel metal-free synthetic method for 2-substituted quinazoline derivatives by the 4,6-dihydroxysalicylic acid-catalyzed oxidative condensation of o-aminobenzylamines and benzylamines using atmospheric oxygen. In this system, the use of a catalytic amount of BF3‧Et2O (10 mol%) as a Lewis acid successfully led to the efficient oxidative condensation and intramolecular cyclization of these amines, followed by aromatization to afford the corresponding 2-arylquinazolines in up to 81% yield with excellent atom economy and environmental factor. Furthermore, to expand this green oxidation method to gram-scale synthesis, we investigated the development of an oxidation process using salicylic acid itself as an organocatalyst, and established a method for the practical green synthesis of a series of nitrogen-containing heterocycles. We expect that the findings will contribute to the development of practical synthesis methods for pharmaceutical manufacturing and industrial applications, along with further advancements in green chemistry.

Photoinduced Syntheses and Reactivities of Phosphorus-Containing Interelement Compounds.

The photoinduced reactions of tetraphenyldiphosphine disulfide with a range of organic dichalcogenides successfully afforded a series of phosphorus(V)-chalcogen interelement compounds via a radical process. The relative reactivities of the organic dichalcogenides (i.e., (PhS)2, (PhSe)2, and (PhTe)2) toward the PIII or PV groups in the diphosphine analogues under light were investigated in detail, and a convenient method was developed to form P-S or P-Se interelement compounds from tetraphenyldiphosphine disulfide and (PhS)2 or (PhSe)2 upon photoirradiation. Furthermore, the relative photochemical properties and reactivities of tetraphenyldiphophine (P-P interelement compound) and its analogues toward photoinduced radical addition reactions were also discussed. The formed P-E (E = S, Se) interelement compounds could be utilized for ionic reactions, and they could be transformed into various phosphine reagents via one-pot processes.

Tris-(4,4'-di-tert-butyl-2,2'-bi-pyridine)(trans-4-tert-butyl-cyclo-hexa-nolato)-deca-µ-oxido-hepta-oxido-hepta-vanadium aceto-nitrile monosolvate including another unknown solvent mol-ecule.

The title hepta-nuclear alkoxido(oxido)vanadium(V) oxide cluster complex, [V7(C10H19O)O17(C18H24N2)3]·CH3CN, was obtained by the reaction of [V8O20(C18H24N2)4] with 4-tert-butyl-cyclo-hexa-nol (mixture of cis and trans) in a mixed CHCl3/CH3CN solvent. The complex has a V7O18N6 core with approximately C s symmetry, which is composed of two VO4 tetra-hedra, two VO6 octa-hedra and three VO4N2 octa-hedra. In the crystal, these complexes are linked together by weak inter-molecular C-H⋯O hydrogen bonds between the 4,4'-di-tert-butyl-2,2'-bi-pyridine ligand and the V7O18N6 core, forming a one-dimensional network along the c-axis direction. Besides the complex, the asymmetric unit contains one CH3CN solvent mol-ecule. The contribution of other disordered solvent mol-ecules to the scattering was removed using the SQUEEZE option in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18]. The unknown solvent mol-ecules are not considered in the chemical formula and other crystal data.

4,6-Dihydroxysalicylic Acid-Catalyzed Oxidative Condensation of Benzylic Amines and Aromatic Ketones for the Preparation of 2,4,6-Trisubstituted Pyridines and Its Application to Metal-Free Synthesis of G-Quadruplex Binding Ligands.

4,6-Dihydroxysalicylic acid was activated under air to catalyze the one-pot oxidative condensation reaction of benzylamines with acetophenones in the presence of BF3·Et2O, affording 2,4,6-trisubstituted pyridines in yields of 59-91%. During this metal-free oxidative condensation reaction, the benzylamines not only provided the aryl moiety at the 4-position of the pyridines but also acted as the nitrogen donor. This method can be applied to the metal-free synthesis of G-quadruplex binding ligands by the sequential addition of 4-chlorobutyryl chloride and pyrrolidine to the reaction system of the 2,4,6-trisubstituted pyridine synthesis.

2,4,6-Trihydroxybenzoic Acid-Catalyzed Oxidative Ugi Reactions with Molecular Oxygen via Homo- and Cross-Coupling of Amines.

Metal-free, oxidative four-component Ugi reactions (U-4CRs) were conducted to synthesize dipeptides from two different amines, isocyanides, and carboxylic acids using 2,4,6-trihydroxybenzoic acid catalyst in O2 atmosphere. The organocatalytic U-4CRs proceed via oxidative cross-coupling of benzylamines with other aliphatic or aromatic amines to form imines, followed by condensation with isocyanides and carboxylic acids. The U-4CRs via cross-coupling of amines are rare, and the simple, metal-free procedures are advantageous for further applications in drug and heterocycle syntheses.